Monodisperse micron-sized polymethylmethacrylate particles having a crosslinked network structure. V

Highly monodisperse micron-sized polymethylmethacrylate (PMMA) particles crosslinked with carboxylic group-containing urethane acrylates (CUA) were produced by simple dispersion polymerization in methanol. In proper condition, CUA employed as a crosslinker had an excellent ability to achieve the monodisperse PMMA particles to the concentration of about 10 wt%. This arose from the fact that CUA formed monomer-swellable primary particles due to its structurally long tetramethylene oxide groups in the molecule. The influence of the concentrations of the initiator and CUA on the particle diameter (D ₙ), particle number density (N ₚ), and polymerization rate (R ₚ) was found to obey the following approximate relationship, D ₙ ∝ [initiator]⁰.⁴¹[CUA]⁻⁰.⁰⁶, N ₚ ∝ [initiator]⁻¹.²² [CUA]⁰.²¹, and R ₚ ∝ [initiator]⁰.³⁴±⁰.⁰³, respectively. The power law dependence of D ₙ and N ₚ on the initiator concentration coincided well with that of linear polymers in the literature. Especially, in this study, it was found that CUA did not have a serious influence on the nucleation. However, the dependence of R ₚ on the initiator concentration was observed to be higher than that of linear polymers, suggesting that uniquely, the solution polymerization process competed with the heterogeneous polymerization during polymerization, because of the crosslinked network structure of the primary particles.